EP0108156B1 - Procédé pour la préparation de polymères non-cristallins de poids moléculaire élevé - Google Patents

Procédé pour la préparation de polymères non-cristallins de poids moléculaire élevé Download PDF

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Publication number
EP0108156B1
EP0108156B1 EP82110099A EP82110099A EP0108156B1 EP 0108156 B1 EP0108156 B1 EP 0108156B1 EP 82110099 A EP82110099 A EP 82110099A EP 82110099 A EP82110099 A EP 82110099A EP 0108156 B1 EP0108156 B1 EP 0108156B1
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Prior art keywords
ether
catalyst
slurry
titanium
crystalline
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Expired
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EP82110099A
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German (de)
English (en)
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EP0108156A1 (fr
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Mark Phillip Mack
Adrian L. Wallace
Lewis B. Decker, Jr.
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ConocoPhillips Co
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Conoco Inc
ConocoPhillips Co
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Priority to EP82110099A priority Critical patent/EP0108156B1/fr
Priority to DE198282110099T priority patent/DE108156T1/de
Priority to DE8282110099T priority patent/DE3279325D1/de
Publication of EP0108156A1 publication Critical patent/EP0108156A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/907—Specified means of reacting components of transition metal catalyst
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T137/00—Fluid handling
    • Y10T137/0318—Processes
    • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

  • This invention relates to a method for preparing ultra high molecular weight, non-crystalline polymers suitable for use as drag reducing substances.
  • a-olefins may be polymerized in the presence of catalysts generally referred to as Ziegler-Natta catalysts.
  • catalysts generally consist of materials such as a transition metal halide such as titanium trihalide and organometallic co-catalysts such as aluminum alkyls or aluminum alkyl halides.
  • a number of ether modified Ziegler-Natta systems have been proposed as catalysts.
  • a propylene polymerization catalyst was taught in US ⁇ A ⁇ 3,116,274, which consisted of an aluminum alkyl, a titanium halide, such as titanium tetrachloride, and an ether compound. This reference recommends the use of a halogen-free alkyl as the co-catalyst for the propylene polymerization process and cyclic ether, such as 1,4-dioxane as suitable catalyst promoters.
  • US ⁇ A ⁇ 3,206,533 prepared synthetic lubricants by the polymerization of a-olefins containing from 6 to 14 carbon atoms in the presence of aluminum alkyl sesquichloride, titanium tetrachloride, and an oxygen-containing organic component, such as an oxirane or methyl alkyl ether, at temperatures of from 0 to 50°C.
  • US ⁇ A ⁇ 3,156,681 revealed an improved process for the polymerization of olefins using an unsaturated ether compound as a catalyst promoter. Suitable unsaturated ethers were taught to be vinyl ethers, with the preferred material being vinyl isobutyl ether.
  • US-A-3,318,859 discloses a process for the stereospecific polymerization of propylene using a catalyst prepared from monoalkyl aluminum halide, violet titanium trichloride and an ether of the formula R I OR 2 , where R, represents alkyl or aralkyl, and R 2 is an alkylaryl, aralkyl, or alkylaryl radical. This reference deals with the preparation of isotactic highly crystalline polypropylene.
  • US-A-3,692,676 reveals a method of reducing friction loss or drag for pumpable fluids through pipelines by adding a minor amount of a very high molecular weight polymer.
  • This reference shows that generally from about 5 to about 50 parts by million (ppm) of a poly-a-olefin in the pumpable fluid provides drag reduction, and defined percent drag reduction for oil being passed through a pipeline as
  • the method of the present invention produces polymers especially well-suited for fluids being transported through pipelines. Further, these polymers may be used as anti-mist agents, fuel efficiency agents, lubricant components and tackifiers.
  • the polymerization is completed or terminated at 20 weight percent or less polymer content, based on total reactor content in order to obtain the ultrahigh molecular weight, non-crystalline hydrocarbon soluble material.
  • the resulting mixture will then contain less than 20 weight percent of the ultrahigh molecular weight polyolefin, a hydrocarbon solvent (or unreacted olefins), deactivated catalyst, and optionally a small amount of alcohol.
  • the entire mixture can then be used as a drag reducing substance.
  • the polymer may be precipitated by a variety of techniques if desired. These techniques are well known to those skilled in this art.
  • materials can be added to prevent deterioration of the mixture or corrosion of its environment. For example; materials such as epoxides (propylene oxide) or compounds containing at least one oxirane unit; primary, secondary, and tertiary amines (such as triethylamine, tributylamine, trioctylamine); polyamines; natural amino acids; and Group I-A and II-A metal hydroxide bases may be added.
  • polymerization is allowed to continue to higher levels, the average molecular weight will rapidly decrease making the materials less desirable for use as drag reducing materials. Therefore, it is preferred in the practice of the present invention to cease polymerization at a polymer content level ranging from 5 to 20 weight percent, again based on total reactor content. However, polymer content levels of from 5 to 15 weight percent are more preferred and polymer content levels of from 8 to 11 percent are most preferred, all based on the total reactor mixture. In addition, as the weight percent polymer content increases, the bulk viscosity of the mixture increases and it becomes difficult to pump these drag reducing materials.
  • the catalyst slurry used in the method of the present invention comprises a crystalline titanium halide material, a hydrocarbon diluent, and a complexing ether agent.
  • the catalyst is titanium trichloride, which is aluminum reduced and activated. Examples of such materials are sold by the Stauffer Chemical Company as TiC1 3 .AA Type 1.1 (aluminum reduced and activated, having the formula TiC1 3 .1/3 (AICI 3 ).
  • the second component of the catalyst slurry is a hydrocarbon diluent.
  • These materials are inactive hydrocarbon solvents with respect to the polymerization. Examples of such materials are straight chain aliphatic compounds or branched hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane or octane. Also suitable are alicyclic hydrocarbons such as cyclohexane, methyl cyclopentane and tetralin. In addition, aromatic hydrocarbons can be used such as benzene, toluene, and xylene.
  • mixtures and analogues of these compounds can be used such as Molex (trademark of Universal Oil Products) raffinate which is a complex mixture of branched aliphatic, cyclic aliphatic, aromatic, and trace amounts (2-3%) of unbranched aliphatic hydrocarbons.
  • the hydrocarbon diluent can also be an a-olefin.
  • the titanium complex and ether agent is a very important component of the catalyst slurry.
  • the ethers are selected from alkyl ethers wherein the ether oxygen is attached directly to 2-aliphatic groups and may have aromatic substituents; aryl ethers wherein the ether oxygen is attached directly to two aromatic groups; aryl-alkyl ethers wherein the ether oxygen is attached directly to one aliphatic and one aromatic group and cyclic ethers wherein the ether oxygen is an integral part of a ring structure.
  • the ether can contain alkyl, aryl, aryl-alkyl or aryl-alkyl groups, each containing from 1 to 30 carbon atoms, and cycloalkyl ethers containing from 2 to 30 carbon atoms.
  • alkyl ethers are benzyl ether, n-butyl ether, tert-butyl methyl ether, di-n-butyl ether, isopropyl ether, and di-n-propyl ether.
  • cyclic ethers are cyclododecane epoxide, cyclohexane oxide, cyclooctene oxide, cyclopentene oxide, dibenzofuran, dihydropyran, furan, 2-methylfuran, 5-methylfuran, 2-methyl tetrahydrofuran, 3-methyl tetrahydrofuran, styrene oxide and tetrahydrofuran.
  • aryl ethers are m-phenoxytoluene and phenyl ether.
  • Representative examples of aryl-alkyl ethers are anisole, butyl phenyl ether, m - dimethyloxybenzene, p - dimethoxybenzene, 2,6 - dimethoxytoluene, 1 - methoxynaphthalene and 2 - methoxynaphthalene.
  • the reaction is normally carried out under an inert atmosphere such as dry nitrogen or dry argon to prevent degradation of the titanium and aluminum alkyl components.
  • the slurry system used in the method of the present invention has a number of processing advantages as well as providing an ultrahigh molecular weight, non-crystalline, hydrocarbon soluble, drag reducing polymer. Initially, the system provides a high safety factor, since titanium trichloride is a flammable solid which decomposes readily by moisture and oxygen to titanium dioxide and hydrogen chloride. The fumes are hazardous, and the catalyst can ignite.
  • the slurry system makes such materials easier to handle, deliver, and meter into the reactor as compared to the solid catalyst. The slurry limits the catalyst exposure to air and moisture.
  • the slurry system provides uniform distribution of catalyst throughout the reactor, reduces the amount of catalyst agglomeration in the preparation of such highly viscous materials and reduces the products' corrosivity on steel and metal surfaces.
  • These catalyst components are normally highly corrosive, and when agglomerated result in a very corrosive environment.
  • the ether complexing agent activates the titanium catalyst and generates a more effective drag reducer.
  • the addition of the ether complexing agent in contact with the titanium component for long periods of time results in catalyst deactivation and/or retardation of product molecular weight.
  • the simple addition of the ether component into the reactor provides improvement.
  • the addition of the ether to the titanium component prior to insertion into the reactor according to the present invention further improves activity and performance.
  • the titanium component is mixed with a hydrocarbon diluent and agitated. This material is then sent to a metering zone wherein materials are passed to a catalyst activation zone where they are contacted with the ether complexing agent and activated.
  • This contact time will generally range up to about 10 minutes, but in any case must be sufficient to activate the titanium material. It is imperative that this activation be carried out under an inert atmosphere and with sufficient agitation to ensure activation.
  • the catalyst activation zone is normally large enough to contain catalyst for several batches. In a more general embodiment the titanium catalyst and ether activator are simply mixed batch-wise for each polymerization carried out.
  • the ether activated titanium component is then charged into a polymerization zone wherein it is contacted with organoaluminum co-catalysts, olefin, and an optional inert hydrocarbon diluent. Under these conditions a very rapid reaction occurs which reduces catalyst agglomeration and which provides a very high molecular weight, non-crystalline hydrocarbon soluble, drag reducing polymer.
  • Figure 1 is a general description of a preferred embodiment of a catalyst slurry activation system.
  • Figure 1 shows the preparation of a catalyst slurry containing crystalline titanium halide in a relatively inert hydrocarbon diluent selected from the group consisting of aliphatic, cycloaliphatic, aromatic hydrocarbons, their halogen derivatives and mixtures thereof in zone 1 entitled "Catalyst Slurry".
  • the slurry contains from 5 to 95 percent by weight TiX n in hydrocarbons.
  • the mixture is stored under inert atmosphere such as dry nitrogen or dry argon to prevent degradation of the TiX n component.
  • inert atmosphere such as dry nitrogen or dry argon
  • a portion of the slurry can be passed through a "Metering Zone” which places the titanium and the inert hydrocarbon diluent into a "Catalyst Activation Zone” in a measured amount.
  • the titanium component is treated with the ether activating or complexing agent.
  • the mole ratio of the ether activating agent to the titanium ranges from 0.01 to 10.0 moles.
  • the catalyst is activated chemically and/or physically prior to polymerization.
  • Contact time forthe catalyst in the activation zone need only be that sufficient for activation of the titanium component and generally ranges from about 1 to about 10 minutes, with from 1 to about 5 minutes being preferred.
  • the preferred slurry concentration in the "Catalyst Activation Zone" ranges from about 10 to about 50% by weight of titanimum component in diluent.
  • the preferred mole ratio of ether to titanium is from 0.4 to 0.7 moles.
  • the activated catalyst is discharged in its entirety into the reaction zone.
  • the reactor already contains the polymerizable olefin and the co-catalyst.
  • a diluent may be present.
  • the polymerization is initiated by the simple introduction of the activated catalyst slurry containing the titanium and ether. It is preferred to contact the co-catalyst in the reactor in the presence of olefin rather than prior to introduction into the polymerization zone, since it has been surprisingly found that this feature provides superior activity and performance for the catalyst as compared combination prior to introduction.
  • Co-catalysts useful in the present invention are aluminum alkyl compounds or alkyl aluminum halide compounds.
  • Representative examples of such materials are trimethylaluminum, triethylaluminum, tri - n - propylaluminum, tri - n - butylaluminum, triisobutylaluminum, tri - n - hexylaluminum, tri(2 - methylpentyl) aluminum, tri - n - octylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diisopropylaluminum chloride, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, di - n - propylaluminum chloride, di - n - butylaluminum chloride, diisobuty
  • the present invention is depicted and exemplified as a batch reaction.
  • the slurry system described is extremely well suited for continuous polymerizations.
  • the titanium catalyst would be continuously contacted with and activated by the ether complexing agent in an activation vessel.
  • the activation vessel would be maintained at a constant volume while a stream of the activated titanium/ether catalyst slurry is passed to the polymerization zone.
  • JP-A-75156586 discloses a method of polymerizing propylene wherein an ether activating agent is added to an organoaluminum compound the olefin prior to inserting titanium.
  • DE-A-2810544 describes a method wherein trichloride and an organoaluminium compound are treated with an alkylaluminum dihalide in butyl ether.
  • JP-A-78129195 shows the presence of aluminum containing compounds with titanium during the activation with ethers. However, these processes are not that described in the present invention.
  • US-A-3,055,878 teaches the use of tertiary amines in preforming a catalyst by reacting said amines with a titanium trichloride. This amine activated titanium material is then added to an olefin and thereafter an organoaluminum material is added.
  • this reference indicates the necessary time of the reaction or activation between the amine compound and the titanium compound is at least one hour and the process produces a crystalline product, not the non-crystalline hydrocarbon soluble materials as obtained according to the present invention.
  • Titanium trichloride (Type 1.1 catalyst from Stauffer Chemical Company) was added under an inert atmosphere of dry nitrogen. The resulting mixture was placed into an agitated under bath (20 ⁇ 1°C) and the catalyst components were allowed to interact for approximatyly 1/2 hour while stirring at 200 revolutions per minute (rpm). The polymerization was initiated by the addition of the olefin, octene-1. No ether activating agent was used.
  • the polymerization was terminated by adding 1.7 milliliters of methanol to deactivate the catalyst.
  • the polymer mixture was stabilized using butylated hydroxy toluene (BHT) as an antioxidant.
  • BHT butylated hydroxy toluene
  • Molex raffinate, DEAC, and di-n-butyl ether were added to a polymerization vessel as in comparative Example No. 2.
  • a 30 weight percent slurry of TiCI 3 .AA from Stauffer Chemical company was prepared in Molex raffinate solvent.
  • the Molex raffinate solvent was sparged with dry nitrogen, and dried over molecular sieves before using.
  • the polymerization was initiated by the addition of the olefin, octene-1. No ether-activating agent was present in the slurry.
  • a 30 weight percent slurry of TiCI 3 .AA in Molex raffinate was prepared as described in comparative Example No. 3. However, the di-n-butyl ether was not added to the DEAC. The ether was added to the slurry containing TiCl 3 .AA in Molex raffinate. The mmole ratio of ether to titanium was 0.56 as was in comparative Examples 2 and 3. The following compounds were used in this experiment: The order of addition was:
  • a 30 weight percent slurry was prepared as described in Example 4 except 0.11 millimoles of di-n-butyl ether per millimole of titanium was added to the slurry, and 0.45 millimoles of di-n-butyl ether per millimole of titanium was added to the polymerization vessel containing Molex raffinate and DEAC.
  • the following components were used in this experiment: The order of addition in this experiment was:
  • the storage tank was maintained at a constant temperature of 23.3°C (74°F) and continuously stirred at low speed.
  • the test fluid flows through a 30.48-cm (1-foot) calming section followed by a 121.9-cm (4-foot) test section where the pressure drop is measured.
  • the pressure drop differences were measured, and the percent drag reduction (%DR) calculated by the equation
  • ⁇ P base is the initial baseline pressure of diesel oil without the additive and ⁇ P additive is the pressure drop with the polymer solution.
  • a 30 weight percent slurry of TiCI 3 .AA in Molex raffinate was prepared which contained 9.04 millimoles of ether per millimole of titanium.
  • the catalyst mixture was agitated then delivered to the polymerization reactor.
  • the reactor contained inert hydrocarbon solvent (Molex raffinate) and DEAC.
  • the mixture was stirred, and 12.5 weight percent octene-1 was added to initiate the polymerization.
  • the mole ratio of polymerization components was 1368/13.4/9.04/1.0 (millimole octene/aluminum/ether/titanium).
  • the resulting catalytic activity at 20° ⁇ 1°C was 41.7 grams poly(octene-1) produced per gram of titanium used per hour.
  • the resulting polymer had an inherent viscosity of 9.9 dl/gm at 300 reciprocal seconds.
  • the mole ratio of ether was varied from 1.13 to 4.52 millimoles per millimole of titanium.
  • a 30 weight percent slurry of TiCI 3 .AA in Molex raffinate was prepared, and the ether was added. Polymerizations were charged with 12.6% octene-1. Ether was added to the slurry before delivering the slurry to the polymerization zone.
  • the ratio of polymerization components (other than ether) in each experiment was 1368/13.4/1.0 (millimole octene/DEAC/titanium). Pertinent results and data on the effect of the ether variations are presented in Table 2.
  • Examples 11 and 12 were carried out to demonstrate the effect of long contact times with the ether component.
  • a slurry of TiCI 3 .AA (30% by weight in Molex raffinate) was prepared. To this mixture was added 1 J mmoles of di-n-butyl ether per mmole of titanium. The slurry was agitated for 15 to 45 minutes prior to the introduction of the slurry into the polymerization zone.
  • the slurry was prepared and stirred for 24 hours prior to introduction into the polymerization zone.
  • the catalyst mixture formed a thick gum prior to introduction. It was difficult to deliver to the reactor zone and results indicated that catalytic retardation took place.
  • the olefin used in each experiment was octene-1 at 12.6% wt.
  • the mmole ratio of catalytic components was 1200/11/1.7/1.0 (mmole octene/aluminum/ether/titanium).
  • the results demonstrate that long contact times of the ether component with a transition metal catalyst are detrimental.
  • the catalyst particle size appeared to be reduced to a state that resulted in catalytic retardation.
  • the preferred activation ⁇ time of the ether component with the titanium component will depend upon the concentration of the ether and the amount of agitation.
  • the ratio in moles of ether to titanium component ranges from 0.01 to 10.0 respectively; however, from 0.01 to 1 are preferred and from 0.25 to 0.75 is most preferred.
  • Contact time can vary substantially, but normally will range from about a few minutes to about 60 minutes. At high concentrations of ether to titanium, that is, above about an equal molar basis, these materials should be left in contact longer than about 60 minutes when using intense agitation. When these precautions are observed, the process of the present invention provides a vastly improved process of obtaining an ultrahigh molecular weight, non-crystalline, hydrocarbon soluble, drag reducing polymer.

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Claims (10)

1. Procédé de préparation de polymères oléfiniques de masse moléculaire élevée par polymérisation d'hydrocarbures a-mono-oléfiniques en présence d'un système catalytique comprenant un catalyseur à base d'un halogènure de titane cristallin répondant à la formule générale TiXn où n=2,5 à 3,0, et X est un halogène, un diluant hydrocarboné inerte, un éther comme agent complexant, et un co-catalyseur, caractérisé en ce que pour préparer des polymères réducteurs de trainée non cristallins, ce procédé comprend les étapes consistant à:
a) préparer une bouillie de catalyseur en mélangeant:
1) au moins 5% en poids, par rapport à la totalité de la bouillie dudit halogénure de titane cristallin avec:
2) lebit diluant hydrocarboné, et en y mélangeant:
3) de 0,01 à 10,0 moles dudit éther comme agent complexant, par mole de titane, en agitant pour activer l'halogénure de titane;
b) mettre en contact la bouillie avec ledit co-catalyseur et un ou plusieurs hydrocarbures a-monooléfiniques contenant de 2 à 30 atomes de carbone, à des températures allant de -25 à 100°C et sous des pressions allant de la pression atmosphérique à 69 bars, pour obtenir un polymère de très haute masse moléculaire qui est soluble dans un diluant hydrocarboné, et,
c) interrompre la polymérisation lorsque la teneur en polymère atteint 20% en poids ou moins, par rapport au contenu total du réacteur.
2. Procédé selon la revendication 1, caractérisé en ce que le co-catalyseur est un aluminium-alkyle ou un halogénure d'organo-aluminium.
3. Procédé selon la revendication 2, caractérisé en ce que l'éther complexant est présent à raison d'un rapport molaire d'environ 0,01 à environ 1,0 par rapport aux moles du chlorure de titane cristallin présent.
4. Procédé selon la revendication 3, caractérisé en ce que le diluant hydrocarboné est une substance ou un mélange de substances choisie(s) parmi des composés aliphatiques à chaîne droite, des hydrocarbures ramifiés, des hydrocarbures alicycliques et des hydrocarbures aromatiques.
5. Procédé selon la revendication 1, caractérisé en ce que le constituant TiXn est le TiCl3.
6. Procédé selon la revendication 1, caractérisé en ce que le constituant TiXn est le TiCl3 préparé par réduction de TiC14 avec de l'aluminium.
7. Procédé selon la revendication 4, caractérisé en ce que:
1) une bouillie catalytique de chlorure de titane cristallin est préparée dans ledit diluant hydrocarboné inerte, et une portion de ladite bouillie est
2) dosée dans une zone de dispersion, où
3) une quantité mesurée de l'éther complexant est mélangée à ladite bouillie en agitant pendant un temps suffisant pour activer ledit chlorure de titane, et
4) la bouillie activée (3) est introduite dans une zone réactionnelle, cette zone contenant au moins l'un desdits hydrocarbures a-mono-oléfiniques et le co-catalyseur, tel qu'un organo-aluminium ou qu'un halogénure d'organo-aluminium.
8. Procédé selon la revendication 7, caractérisé en ce que l'éther complexant est choisi parmi les éthers di-n-butylique, benzylique, diéthylique, diisopropylique, di-n-propylique, diphénylique, l'anisole, l'éther butyl phénylique, le 1-éthoxynaphtalène, le 1-méthoxynaphtalène, le 2 - méthoxynaphtalène, le tétra- hydrofurane, le 1,4-benzodioxane, le 2,3 - benzofurane, l'éther tert-butyl-méthylique, et des mélanges de ceux-ci.
9. Procédé selon la revendication 7, dans lequel le constituant TiXn est le TiCl3.1/3 AICI3.
EP82110099A 1981-05-07 1982-11-02 Procédé pour la préparation de polymères non-cristallins de poids moléculaire élevé Expired EP0108156B1 (fr)

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Application Number Priority Date Filing Date Title
EP82110099A EP0108156B1 (fr) 1981-05-07 1982-11-02 Procédé pour la préparation de polymères non-cristallins de poids moléculaire élevé
DE198282110099T DE108156T1 (de) 1981-05-07 1982-11-02 Verfahren zur herstellung von nicht kristallinen polymeren mit hohem molekulargewicht.
DE8282110099T DE3279325D1 (en) 1981-05-07 1982-11-02 Improved method for the preparation of non-crystalline polymers of high molecular weight

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Application Number Priority Date Filing Date Title
US06/261,339 US4358572A (en) 1981-05-07 1981-05-07 Method for the preparation of non-crystalline polymers of high molecular weight
EP82110099A EP0108156B1 (fr) 1981-05-07 1982-11-02 Procédé pour la préparation de polymères non-cristallins de poids moléculaire élevé

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EP0108156A1 EP0108156A1 (fr) 1984-05-16
EP0108156B1 true EP0108156B1 (fr) 1989-01-04

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US (1) US4358572A (fr)
EP (1) EP0108156B1 (fr)
JP (1) JPS5986606A (fr)
CA (1) CA1189246A (fr)
DE (1) DE108156T1 (fr)
NO (1) NO160449C (fr)

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Publication number Priority date Publication date Assignee Title
WO1995000563A1 (fr) * 1993-06-18 1995-01-05 Conoco Inc. Suspension polymere soluble dans l'huile, sans solvant, permettant de reduire le frottement
US5869570A (en) * 1996-03-19 1999-02-09 Energy & Environmental International, L.C. Composition of and process for forming polyalphaolefin drag reducing agents

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Publication number Priority date Publication date Assignee Title
US4433123A (en) * 1979-01-29 1984-02-21 Conoco Inc. Polymerization process for drag reducing substances
AU2765084A (en) * 1983-07-13 1985-01-17 Conoco Inc. Alpha-olefin catalyst
US4518757A (en) * 1983-12-23 1985-05-21 Exxon Research & Engineering Co. Drag reduction agent for hydrocarbon liquid
US4613712A (en) * 1984-12-31 1986-09-23 Mobil Oil Corporation Alpha-olefin polymers as lubricant viscosity properties improvers
US4881566A (en) * 1988-10-11 1989-11-21 Conoco Inc. Method for reducing pressure drop in the transportation of drag reducer
US5028574A (en) * 1988-11-14 1991-07-02 Conoco Inc. Composition and method for friction loss reduction
US4945142A (en) * 1988-11-14 1990-07-31 Conoco Inc. Composition and process for friction loss reduction
US4952738A (en) * 1988-11-14 1990-08-28 Conoco Inc. Composition and method for friction loss reduction
US5539044A (en) * 1994-09-02 1996-07-23 Conoco In. Slurry drag reducer
US6015779A (en) 1996-03-19 2000-01-18 Energy & Environmental International, L.C. Methods for forming amorphous ultra-high molecular weight polyalphaolefin drag reducing agents
US6093833A (en) * 1999-01-14 2000-07-25 Akzo Nobel N.V. Process for producing trivalent titanium coordination complex
FI111735B (fi) * 2000-10-27 2003-09-15 Fortum Oyj Menetelmä virtausvastusta vähentävän aineen valmistamiseksi ja sen käyttämiseksi
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NO160449B (no) 1989-01-09
DE108156T1 (de) 1984-09-27
NO160449C (no) 1989-04-19
JPS5986606A (ja) 1984-05-18
NO823681L (no) 1984-05-07
US4358572A (en) 1982-11-09
CA1189246A (fr) 1985-06-18
EP0108156A1 (fr) 1984-05-16

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